Production of trisazo dyestuffs



Patented Aug. 19, 1941 UN I-TED STATES PATENT OFFICE PRODUCTION OFTRISAZO DYESTUFFS Pierrna-nn' Winkel'er, Schkopau, Albert Peta,Mannheim; Wer'n'er Keller, Dessau, and Ludwig Neumann, Mannheim,Germany, assignors to General Aniline & Film Corporation, acorporationlof Delaware I'IrGe'rmany July 23, 1938 8 Claims. (01.260-173) The present invention relatesto trisazo dyestuffs.

We have found that violetor blue to green or black trisazo dyestufis ofthe following general formula have very advantageous tinctorialproperties j a A-N:N-B1-N N-B2N=-ND in which A is the radical of anaromatic ortho-v hydroxycarboxylic, acid, B1 and B2- are aromatic oraromatic-heterocyclic radicals and D is the radical: ofanaminohydroxynaphthalene sulionic acid the amino group of which isunited with an aromatic radical containing a carboxylic acid group and ahydroxy group in ortho-position to each other. The new dyestuffspreferably contain at least two sulfonic acid groups.

Trisazo dyestuffs of the said; kind may be prepared for example in thefollowing; manner: An aminohydroxybenzeneor na'phthalene-orthocarboxylicacid, as for example l-amino-Z-hydrcXyben'zene-3 oarboxylic acid;l-amino i-hydroxybenzenei-3wcarboxylicv acid or their homologues, aswelllas the'sulfonicfaclds derived therefrom, or also an aminobenzoyloraminobenzenesulfonyl-aminohydroxybenzeneor-naphthalene-orthot-carboxylic acid or a sulfonic acid of the same, isdiazotized (radical A) and coupled withan aromatic oraromatic-heterocyclic amino compound capable of being coupled (radicalB") amino-2.5-dimethylbenzene, l amino-2-methoxy-5-rnethylbenzene,l-aminonaphthalene, 1'-" of an aromatic ortho hydroxycarboxylic acid(radical D). The said hydroxycarboxylic acid radical may be directlyattached to the amino group, as for example in' N-hydroXycarboxy-'phenyl-Z-amino-5-hydroxynaphthalene 7 sulfonic acid, or also by a bridgeto the aminogroup, such as in N-hydroxycarboxylphenylsulfonyl 2- amino-EhydrOXynaphthalene '7 sulfonic acid and N-substitution products thereof,or N-hy-- as for example l-amino-3-mcthylberiziane, 1'-'droxycarboxyphenylsulfonybNrmethyle2ramino- 8hydroxy-naphthaleneefiesulfonic acidzorl NJ-hy-1droXycarboiiyphenylsulfonyl-Neethy1=l-aminor8-hydroxynziphthalerie-B.Bedisulfonic acid.

The an'iinodisazo dyestuff may: alsol'be preparediby coupling diazotizedni-tro amino benzenes: or mono-asyl-diaminobenzenes withhan' aminocompound capable of coupling, coupling the diazo compound of theresulting aminoazo dyestuff with an orthoehydroxycarboxylic acid capablecfcoupling and reducing the nitro. group or saponifying theacylaminogroup.

The new dyestuffs may also be prepared by diazotizing amino azodyestuffs of theformula The new trisazo dyestuffs dye violet or blue toness of dyeingsthus produced maybe improved by aftertreatment with:copper or chromium salt solutions. v

The following examples will further illustrate how-this invention may becarried out in practice but the; invention is not restricted to theseexamples. The parts areby weight.

" Example 1 233 parts of l-amino-2-hydroxy-3 carboXybenzene-5-sulfonicacid are dissolved in sodium carbonate solution, Gil-parts ofsodiumnitrite are added; and ice and hydrochloric acid are allowed to run intothe mixture. unitedywit'h a soda-alkaline solution of 223 par-ts of1;eaminonaphthalene-T-sulionic acid and-after the addition of: sodiumacetate I coupled in acetic acid. Thelwhole is stirred. for some time,sodium carbonate is added until a soda-alkaline reaction is produced andthe aminoazo' dyestuff is diazot'iz'ed also by allowing the dyestufi;solution to which sodium nitrite has'been added to into hydrochloric,acid andtlien adding sodium acetate untilan, acetic acid reaction is}obtained;

' The diazoicompound isthen filtered off bysuction' and unitedwi-th afurther 223 parts of 1-- The d-iazo solution isaminonaphthalene-7-sulfonic acid in the form of the sodium salt to formthe aminodisazo dyestuif. The sodium salt of this dyestuif whichseparates is filtered off by suction, diazotized in the usual manner andcoupled alkaline with 343 parts of N l-hydroxy-3-carboxyphenyl 2amino--hydroXynaphtha1ene-7-sulfonic acid:

to form the trisazo dyestufi". It is salted out, filtered off bysuction'and dried. The trisazo dyestuff yields blue shades having goodfastness properties on cotton.

Example 2 In a manner similar to that described in Example 1, thefollowing dyestuff is prepared: 1- amino-3-carboXy-4'-hydroxybenzene-5-sulfonic acid is diazotized and coupled with l-aminonaphthalene, further diazotized and coupled with1-aminonaphthalene-'l-sulfonic acid, again diazotized and, coupled withN-4-hydroxy-3'- carboxyphenyl-2 amino-5-hydroxy-naphthalene- 7-su1fonicacid. The trisazo dyestuif dyes vegetable fibres blue shades thefastness to washing of which is excellent after treatment with chromicsalt solutions.

* Example 3 352 parts of N-B'-aminobenzoyl-1-amino-3-carboxy-4-hydroxybenzene-5-sulfonic acid are dissolved in aqueouscaustic soda solution, 69 parts of sodium nitrite are added and it isallowed to run into dilute hydrochloric acid at 20 C. A neutral solutionof 223 parts of l-aminonaphthalene-'l-sulfonic acid is then added andthe'coupling completed by the addition of sodium acetate. The aminoazodyestufi which separates is dissolved by the addition of caustic sodasolution, 69 parts of sodium nitrite are added and diazotizationeffected by the addition of hydrochloric acid. After several hours, aweakly hydrochloric acid solution of 143 parts of 1-amino naphthalene isadded and coupling to the disazo dyestuff effected while stirring. It isfiltered ofi by suction, taken up in dilute caustic alkali solution,cooled, 69 parts of sodium nitrite are added and then hydrochloric aciduntil the reaction is weakly acid. The resulting diazo compound isallowed to run into an alkaline solution containing 375 parts of N-l'-hydroxy-3-carboxyphenyl- 2-amino-5-hydroxynaphthalene-7-sulfonioacid.

The trisazo dyestufi thus obtained yields on cotton and viscoseartificial silk a blue which acquiresan excellent fastness to washing byaftertreatment with chromic salt solutions.

Example 4 The monoazo dyestuff of the foregoing example is, as thereindescribed, further diazotized and coupled with a neutral solution of 223parts of 1-aminonaphthalene-7-sulfonic acid, with an addition of sodiumacetate, to form the disazo dyestuff. The solution is rendered alkalineand the disazo dyestufi is salted out, filtered 01f by suction, broughtinto solution again by the addition of alkali hydroxide and 69 parts ofsodium nitrite are added while cooling with ice and the compounddiazotized by the addition of hydrochloric acid. until the reaction isweakly acid. The diazo compound is allowed to run into an alkalinesolution of 453 parts ofN-4'-hydroxy-3-carboxyphenyl-1'-sulfonyl-N-methyl 2 amino 5hydroxynaphthalene-7-sulfonic acid:

II. 13038 N sOQOH COOH l CH3 OOOH III. H035 be used as the last azocomponent, blue-grey shades of excellent fastness properties areobtained.

By selecting as end component, N-4'-hydroxy-3-carboxyphenyl-1'-sulfonyl-N-ethyl-1 amino-8-hydroXynaphthalene-3.6-disulfonic acid:

a dyestufi is formed which dyes the fibre silvergrey shades which may befurther improved considerably in their fastnessv properties byaftertreatment with chromic salt solutions.

Example 5 A weak hydrochloric acid solution of 121 parts of1-amino-2.5-dimethylbenzene is added to the diazo compound of 352 partsof N-3-aminobenzoyl-l-amino 3 carboxy 4 -hydroxybenzene-' 5-sulfonicacid, coupling to the monoazo dyestuff being effected with the additionof sodium acetate. The monoazo dyestuif is dissolved with the additionof caustic soda solution, 69 parts of sodium nitrite are added and thenhydrochloric acid until there is a weak acid reaction, the whole thenbeing stirred for some time at about 5 C.

The diazo compound is then coupled with a neutral solution of 267 partsof 1-amino-2- ethoxynaphthalene-6-sulfonic acid with an addition ofsodium acetate. After completion of the coupling, the whole is renderedalkaline, salted out and the disazo dyestuif separated. It is dissolvedin soda solution, 69 parts of sodium nitrite are added while coolingwith ice and the whole slowly acidified with hydrochloric acid. Aftercompletion of the diazotization, it is coupled with 54'lparts ofN-4'-hydroXy-3'-carboxyphenyl-1-sulfonyl-N -ethyl-1-amino-8-hydroxynaphthalene-3.S-disulfonic acid (Formula IV) in ammoniacal solutioncontaining pyridine.

The dyestuif yields on cotton or viscose artificial silk blue-greenshades which after treatment with chromic salt solutions have remarksable fastness to washing. I i

methyl- 2-amino 8 -hydroxynaphthalene- 6' sulfonic acid (Formma I-1n 25-parts; (if-sodium car- Example 6 I lhe. diam compound. of i 352 parts of3.-aminobenzoyl-r-amino 3 ca rboxy 4- h-ydroxybenzene- 5-su1 fonic acidis coupled with 189v parts of 1- (lf-aminophenyl)-3-methyl-5-pyrazolone' tio'n, salted outl and filtered ofi by suction.The.

disazo dyestufi isitakenup with water, 69 parts of sodium nitrite" are.added and. diazotization. effected by the slow addition of hydrochloric.acid at about 8 C. It is then coupled with 547 parts of N4 -hydroxy-3-carboxyphenyl-1'-sulfonyl- N ethyll -amino-8 -hydroxynaphthalene- 3 .6-disulfonic acid (FormulaIV) in ammoniacal solution containing pyridine.The dyestuff yields clear green dyeings which become eminently fast towashing by aftertreatment for example with chromicfluoride.

Example 7 47.6 parts of 3- or 4-aminobenzoyl-1-amino-2-hydroxy-3-carboxy-benzene-fi-su1fonic acid are diazotized and coupled inacetic acid solution with 22.4 parts of 1-aminonaphthalene-7-sulfonicacid. The resulting azo dyestuff is diazotized and the diazo compoundcoupled with 30 parts of 1-aminonaphthalene-7-su1fonic acid.

The disazo dyestuff is then salted out and filtered oil. It is thendissolved in sodium carbonate solution and diazotized by the addition ofsodium nitrite and introduction of the mixture into dilute hydrochloricacid. The resulting diazo compound is filtered off and introduced at C.into a solution of 59 parts of N-4-hydroxy- 3 carboxyphenyl 1sulfonyl-N-methyl 2 amino--hydroxynaphthalene-7-sulfonic acid (FormulaII) to which 60 parts of pyridine and 57 parts of per cent ammonia havebeen added.

After completion of the coupling the Whole is heated and the trisazodyestuff salted out. dyes cotton and viscose artificial silk blue-greenshades. By aftertreatment with chromic salt solutions, an excellentfastness to washing of the dyeing is obtained.

By using l-aminonaphthalene as the second coupling component instead ofl-aminonaphtha- 1ene-7-sulfonic acid, a similar dyestuff is obtained.

Example 8 The diazo compound of the disazo dyestuff according to Example7 from 47.6 parts of 4-aminobenzoyl-glsamin0-2 hydroxy-3-carboxyphe'nyl-5-sulfonic acid, 22.4 parts of l-aminonaphtha- 1ene-7-sulfonic acid, andparts of 1-aminonaphthalene-Y-sulfonic acid is introduced into anaqueous solution containing 60 parts of N- 4 -hydroxy- 3 '-carboxyphenyl1 '-sulfonic-'N with an; addition of sodium acetate. .After completionbonate and 30 parts of pyridine. After coupling is completed, the wholeis heated and the dyestufi salted out with sodium chloride. It goes onto cotton and viscose artificial silk with a bluish g'reyj color; Byaftertreatment" with chromic salt solutions; a' considerableincrease inthe fastness to washing. is obtained.

Example 9 A75- parts of -4' aminobenzoyl-1-amino-2 hydroxy- 3carhoxybenzene-5-sulfonic acid are diazo-tized and coupled in thepresence of acetic acid with 22.4- parts; of l -a-minonaphthaleneflsulfonic acid; The resulting aminoazo dyestuff is then diazotized andcoupled in acetic acid solution with 13.3 parts of I-aminonaphthalene.After completion of the coupling, the disazo'dyey stuff is:filtered off,dissolved in soda solution and diazotized. The diazo compound is thenintroduced into asolution of N4'-hydroxy-3-carboxyphenyl-2-amino-5h'ydroxynaphthalene- 7 sulfonic acid (Formula I) in 200 parts of water,

. 55parts of ammonia. and 20 parts of pyridine.

After completion ofithe coupling, the whole is heated and the dyestuff.salted out. Itdyes cotton andviscoseartificial silk greenish blue shadesof color. The dyeings which have been after- I treated with chromic'salt solutions have a very good fastness to washing.

What we claim is:

1. Azo dyestuffs corresponding to the general formula A-N=N'-B1N' N"B2N=N D" in which A stands for the radical of an aromatic ortho-hydroxycarboxylic acid selected from the group consisting of the benzene andnaphthalene series, B1 and B2 stand for members of the group consistingof radicals of the benzene and naphthalene series and phenyl pyrazoloneradicals and. D stands for the radical of an aminohydroxynaphthalenesulfonic acid coupled alkaline the amino group of which is united with aradical of the benzene series containing a carboxylic acid group and ahydroxy group in ortho-position to each other.

2. Azo dyestuffs corresponding to the general formula AN:NB1N=NB2N=ND inwhich A stands for the radical of an orthohydroxycarboxyphenyl sulfonicacid, B1 and B2 stand for members of the group consisting of radicals ofthe benzene and naphthalene series and phenyl pyrazolone radicals and Dstands for the radical of an aminohydroxynaphthalene sulfonic acidcoupled alkaline the amino group of which is united with a radical ofthe benzene series containing a carboxylic acid group and a hydroxygroup in ortho-position to each other.

3. Azo dyestufis corresponding to the general formula in which A standsfor the radical of an orthohydrocarboxyphenyl sulfonic acid, B1 and B2stand for members of the group consisting of radicals of the benzene andnaphthalene series and phenyl pyrazolone radicals and D stands for theradical of a 2-amino-5-hydroxy-naphtha- 1ene-7-sulfonic acid attached tothe azo group shown in 6-position, the amino group being united with aradical of the benzene series containing a carboxylic acid group and ahydroxy group in ortho-position to each other.

' 4. Azo dyestuffs corresponding to the general formula V inwhich A'stands for the radical of an ortho-e hydroxycarboxyphenyl sulfonic acid,B 1 and B2 stand for members of the group consisting of radicals of thebenzene and naphthalene series and phenyl pyrazolone radicals and Dstands for the radical of a 2-amino-8-hydroxynaphtha1ene- 6-sulfonicacid attached to the azo group shown in 7-position, the amino groupbeing united with a radical of the benzene series containing acarboxylic acid group and a hydroxy group in orthoposition to eachother.

5. Azo dyestuifs corresponding to the general formula A--N=NB1N=N-B2N=N--D in which A stands for the radical of anorthohydroxycarboxyphenyl sulfonic acid, B1 and B2 stand for naphthaleneradicals attached to the azo groups shown in 1-' and 4-position, and Dstands for the radical of a 2-amino-5-hydroxynaphthalene-'l-sulfonicacid attached to the azo group shown in fi-position, the amino groupbeing united with a radical of the benzene series containing acarboxylic acid group and a hydroxy group in ortho-position to eachother.

7. Azo dyestuffs corresponding to the general formula in which A standsfor the radical of an orthohydroxycarboxyphenyl sulfonic acid, B1 and B2stand for naphthalene radicals attached to the azo groups shown in 1-and l -position, and D stands for the radical of a2-amino-5-hydroxynaphthalene-'Z-sulfonic acid attached to th azo groupshown in fi-position, the amino group being united with the radical ofsalicyclic acid.

8. Azo dyestuffs corresponding to the general formula e JJOOH in which Astands for the radical of an orthohydroxycarboxyphenyl sulfonic acid andB1 and Bz stand for naphthalene radicals attached to the azo groupsshown in 1 and 4-position.

HERMANN WINKELER. ALBERT PETZ. WERNER KELLER. LUDWIG NEUMANN.

